JPH02308891A - Light-shielding material - Google Patents

Abstract

PURPOSE:To provide a light-shielding material containing a heterolytic ion splitting spiro-photochromic compound and an aromatic carboxylic acid salt capable of forming ampholytic counter ions and having excellent weather resistance and durability of coloring stability. CONSTITUTION:The objective material contains (A) a heterolytic ion splitting spiro-photochromic compound (e.g. spiropyrans, spirothiopyrans, spirooxazines, spironatphthoxazines, etc.) and (B) a bivalent metal salt of an aromatic carboxylic acid capable of forming ampholytic counter ions (preferably zinc salt, nickel salt, etc. of 2-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a light-shielding material for adjusting the amount of transmission of sunlight, etc., using a compound exhibiting organic photochromic properties, and in particular, to a light-shielding material that uses a compound exhibiting organic photochromic properties. The object of the present invention is to provide a light-shielding material with excellent durability and significantly improved coloring stability.

<Prior art> Many substances are known as organic compounds that exhibit photochromism, but the most commonly studied are:
It is a spirophotochromic compound typified by spiropyran compounds.

When such a compound is irradiated with ultraviolet rays, it causes heterolic ion dissociation and develops a color, and when heated or irradiated with visible light, the color disappears and returns to its original state. This phenomenon occurs repeatedly. .

The phenomenon of reversible color change when exposed to light is called photochromism, and a product that actually takes advantage of this phenomenon and is widely available on the market is an eyeglass lens in which silver halide, an inorganic substance, is dispersed in glass. There is.

On the other hand, organic photochromic compounds do not have sufficient light resistance or color stability, so they are not suitable for light-shielding materials that require durability, and have hardly been put into practical use. It was something.

Deterioration of organic photochromic compounds is thought to be caused by light and oxygen, and various studies have been conducted to prevent this deterioration.

For example, those with added antioxidants (Japanese Patent Application Laid-Open No. 58-11
3203), UV absorber added (YSP
32t2898, etc.), - As a heavyt oxygen deactivator, amines such as hindered amines, or nickel-based metal complexes are added (% 173181. 252496) etc. are known.

<Problems to be Solved by the Invention> However, in the above-mentioned improved technology, when an acid monoxide inhibitor is added, it is not expected to have much of an effect on improving light resistance, and when an ultraviolet absorber is added, photochromic However, the organic photochromic compound has drawbacks such as lowering the properties of the organic photochromic compound and promoting deterioration of the organic photochromic compound. Also, -
It is a heavytate acid quencher. Products containing amines or metal complexes may be colored even when dispersed in a colorless and transparent resin binder, or may not have sufficient compatibility with the resin binder, while their light resistance may be poor. It was something that didn't exist.

Therefore, it is an object of the present invention to provide a light-shielding material using an organic photochromic compound that has a high degree of light resistance, excellent coloring stability, and durability without reducing the photocoloring function. That is.

Means for Solving the Problems> That is, the present invention provides l) a light-shielding material containing a heterolytic ion-cleavable spirophotochromic compound and a divalent metal salt of an aromatic carboxylic acid forming an amphoteric counterion; 2) In the preceding item, the light-shielding material contains 5 or more molar equivalents of the divalent metal salt of the aromatic carboxylic acid per 1 molar equivalent of the spirophotochromic compound; A light-shielding material in which the divalent metal salt of an acid is a divalent metal salt of an aromatic carboxylic acid selected from hydroxybenzoic acid, phthalic acid, hydroxynaphthoic acid, or naphthalene dicarboxylic acid, 4) the aromatic aroma of item 3 above; 5) a light-shielding material in which the group carboxylic acid is any one of 2-hydroxybenzoic acid, l-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, and 2-hydroxy-3-naphthoic acid; 5) the first light-shielding material; 3) A light-shielding material in which the divalent metal salt of an aromatic carboxylic acid is a metal salt of zinc or nickel; 6) The light-shielding material of item 1 above is dissolved or dispersed in an organic binder, and the divalent metal salt of an aromatic carboxylic acid is disposed on a support. The purpose is to provide a light-shielding article formed by applying the same.

First, a typical heteroliptic ion-cleavable spirophotochromic compound used in the light shielding material according to the present invention can be represented by the following general formula.

More specifically, in the above general formula 〇), X is CM,
Spiropyran compound where Y is 0 atom, x is ca, y
Examples include spirothiobilane compounds where X is an S atom, spirooxazine compounds where X is an N atom and Y is an O atom, and spironaphthoxazine compounds.

In the general formula [I], the substituents on the aromatic ring represented by aIA and ring B include an alkyl group, an alkoxy group, an alkoxycarbonyl group, a haalkoxysulfonyl group, an alkylphenol group, a halogen atom, and a nitro group. I can give an example.

The above-mentioned spirophotochromic compounds have different hues in the coloring state, that is, light absorption ranges, depending on their structures and types of substituents, and it is necessary to select or use them in combination according to the purpose of light shielding. .

Among these spirophotoclock compounds, spirooxazine and spironaphthoxazine compounds are superior in light resistance to spiropyran compounds, and spirothiobilane compounds have a coloring wavelength of 70O
Since it has higher absorption characteristics than Im, it is suitable for light shielding applications including heat ray absorption.

When these spirophotoclock compounds are irradiated with ultraviolet rays, they show the following heterolytic cleavage properties: In the case of spiropyran compounds and spirooxazine compounds: Colorless state In the case of spirothiopyran compounds: Color development The color is erased by visible light irradiation or heat.

By using these spirophotochromic compounds alone or in combination, the hue of the coloring state and the amount of light absorption can be controlled arbitrarily, and they block visible light and near infrared rays in the range of 400 nm to 700 nm or 700 nm or more. It is something that can be done.

In addition to the above-mentioned compounds, spirofortchromic compounds according to the present invention include dimers, trimers, etc. of these compounds, and polymers obtained by introducing a polymeric vinyl group into the above-mentioned compounds and polymerizing them. Objects can also be used in the same way.

The divalent metal salt of an aromatic carboxylic acid that forms the amphoteric counterion that is one of the components is a divalent metal salt of an aromatic acid that has a hydroquine group and a carboxyl group or two carboxyl groups in the molecule. Specific examples include metal salts of zinc, nickel, copper, cobalt, etc., such as hydroxybenzoic acid, phthalic acid, hydroquinaphthoic acid, and naphthalene dicarboxylic acid.

Among others, 2-hydroxybenzoic acid (salicylic acid), 1-
Human 10x-2-naphthoic acid, 2-hydroxy-1-
Divalent metal salts of naphthoic acid and 2-hydroxy-3-naphthoic acid are preferred, and among the divalent metals, metal salts of zinc and nickel are particularly preferred.

After reaching a saturated color density by irradiation with ultraviolet rays, it exhibits the behavior of fading when irradiated with light, and its stability and light resistance in the coloring state are extremely low. When the specified compounds are combined, either no light transmission behavior is exhibited or a remarkable fading inhibiting effect is exhibited. In addition, in terms of thermal decolorization behavior, spirophotochromic compounds alone exhibit rapid decolorization behavior, but the system of the present invention has extremely high coloring stability and does not easily decolorize under weak indoor light. It is.

In the colored state of the spirophotochromic compound, that is, in the heterolytic ion dissociation state, the metal salt of the aromatic carboxylic acid that forms the amphoteric counterion is considered to contribute to stabilizing the ionic dissociation state. For example, in the case of zinc salt of salicylic acid, it would be like light l.

In addition, in the light-shielding material according to the present invention, the mixing ratio of the spirophotochromic compound and the metal salt of aromatic carboxylic acid is such that the latter is 5 and a half moles or more, more preferably 10 moles or more, per 1 mole equivalent of the former. By using an equivalent amount or more, light resistance and coloring stability can be maintained even higher.

When combining the two types of compounds described above to form the desired light-shielding material, use an appropriate solvent and organic binder.
A light-shielding material can be obtained by dissolving or dispersing the light-shielding material into a coating agent, etc., and coating it on a suitable support or forming a film without using a support.

The organic binder used in the present invention may be one that has good compatibility with the above-mentioned compounds, is optically transparent, and has excellent film-forming ability; specifically,
Acrylic, styrene, vinyl acetate, polybutyral, cellulose, vinyl chloride, vinylidene chloride, polyolefin polymers or copolymers, polyurethane resin, polycarbonate resin, epoxy resin, phenolic resin, polyester Examples include resin.

In addition, the organic solvents to be dissolved include alcohols such as methanol, ethanol, and isopropyl alcohol;
Ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers such as ethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate and n-butyl acetate, as well as benzene, chlorobenzene,
Toluene, xylene, n-hexane, cyclohexane,
Acetonitrile, dimethylformamide, dimethylsulfokide, chlorocyrm, methylene chloride, 1,2-dichloroethane, trichloroethylene, carbon tetrachloride, and mixtures thereof can be used.

There are plastic materials such as tate, polycarbonate, regular paper, baryta paper, glass, metal, etc.

The spirophotochromic material according to the present invention and the metal salt of the aromatic carboxylic acid are dispersed in the binder and organic solvent described above, and the mixture is coated on the support and dried, or
Alternatively, a light-shielding material can be obtained by making it into a film without a support, but if necessary, conventionally used antioxidants, ultraviolet absorbers, and -1
It is possible to add an oxygen deactivator or the like.

The light-shielding material according to the present invention can be light-modulated by blocking not only visible light but also light in the near-infrared region by selecting the type of spirophotochromic compound or by combining spirophotochromic compounds with different light absorption characteristics in the colored state. It becomes possible. Note that the light-shielding material of the present invention has excellent stability in a colored state, and therefore does not easily discolor by irradiation with natural visible light. Alternatively, it is possible to arbitrarily erase the color by taking measures to control electrochemical oxidation and reduction reactions to impart electroclockability.

<Example> Spiropyran compound shown in Example 1 3.59 (0,01
mol), salicylic acid 25g (0,t5 mol) and polymethyl methacrylate (SumiPex BMR manufactured by Sumitomo Chemical Co., Ltd.
) and 225 g of a 1:1:1 mixed solvent of butyl acetate, toluene, and butanol were added to prepare a coating agent, which was applied onto an optically polished glass plate and dried to obtain a light-shielding material 1.

Example 2 The same spiropyran compound as in Example 1 was mixed with zinc salt of l-hydroxy-2-naphthoic acid in the same molar ratio to prepare a coating agent in the same manner as in Example 1, and the coating agent was applied and dried on a glass plate to produce a light-shielding material. I got 2.

Spirooxazine compounds shown in Examples 3-4 3.31 (0,
01 mol), 3310.15 mol) of the zinc salt of l-hydroxy-2-naphthoic acid (Example 3), and 33 g (0.15 mol) of the zinc salt of 2-hydroxy-2-naphthoic acid (example 3). Example 4) were mixed respectively to prepare a coating agent in the same manner as in Example 1, and the coating agent was applied onto a glass plate and dried to prepare light shielding materials 3 and 4.

Comparative Examples 1 to 2 Comparative light-shielding materials 1 and 2 were created by using the coating agents of Examples 1 and 3 to which the zinc salt of aromatic carboxylic acid was not added, and applying and drying them on a glass plate. did.

[Evaluation test l]

Using the light shielding materials obtained in Examples 1 to 4 and Comparative Examples 1 to 2,
We exposed each compound to ultraviolet light for 150 hours using a weather camera equipped with a carbon arc lamp manufactured by Suga Test Instruments, and measured the residual optical density relative to the optical density at the maximum absorption wavelength for saturated color development using a spectrophotometer. was evaluated.

On the other hand, in order to evaluate the stability of the tinting strength in the dark, the residual optical density was measured in the same manner when the sample was left in the dark for 48 hours. The evaluation results are shown in Table-1.

Table-1 Examples 5 to 7 With respect to 1 molar equivalent of the spirooxazine compound used in Example 3, the mixing ratio of zinc salt of l-hydroxy-2-naphthoic acid was 5 molar equivalent (Example 5), The amount was changed to 10 molar equivalents (Example 6) and 20 molar equivalents (Example 7), coating agents were prepared in the same manner, and coated on a glass plate and dried to obtain light shielding materials 5 to 7.

Evaluation Test 2 Similarly to Evaluation Test 1, the light resistance and coloring stability of the light shielding materials of Examples 5 to 7 and Comparative Example 2 were investigated, and the results are shown in Table 2.

Table 2 Effects> As specifically shown in the examples above, the light-shielding material according to the present invention has significantly improved light resistance and coloring stability compared to the case of using a spirophotochromic compound alone. It is.

In addition, the light resistance and coloring stability mentioned above are greatly influenced by the mixing ratio of the spirophotochromic compound and the aromatic carboxylic acid that forms the amphoteric counterion, and the latter is at least 5 molar equivalents of the former. , more preferably 10 molar equivalents or more is necessary in order to obtain a light-shielding material with excellent durability.

Therefore, according to the present invention, by selecting the type of compound used, the light absorption characteristics in the coloring state can be adjusted from the entire visible light range to near the near infrared.
It can be used as a highly durable light-shielding material for building materials such as window glass, or for controlling light transmission in window glass for vehicles such as automobiles. In addition, since the coloring state is extremely stable and it is not easy to erase the color with visible light such as indoor light, forced color erasing means, such as thermal means or electrochemical means such as imparting electrochromic properties, are required. By using them together, it is also possible to artificially control color development and decolorization.

#fc+f-appearance person Sakata Inx Co., Ltd. (outside 3
given name)

Claims (1)

[Scope of Claims] 1) A light-shielding material characterized by containing a heterolytic ion-cleavable spirophotochromic compound and a divalent metal salt of an aromatic carboxylic acid that forms an amphoteric counterion. 2) The light-shielding material according to claim 1, wherein the divalent metal salt of the aromatic carboxylic acid is contained in an amount of 5 molar equivalents or more based on 1 molar equivalent of the spirophotochromic compound. 3) In claim 1, 2 of the aromatic carboxylic acid
1. A light-shielding material, wherein the valent metal salt is a divalent metal salt of an aromatic carboxylic acid selected from hydroxybenzoic acid, phthalic acid, hydroxynaphthoic acid, or naphthalene dicarboxylic acid. 4) The aromatic carboxylic acid of claim 3 is any one of 2-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, and 2-hydroxy-3-naphthoic acid. A certain light-shielding material. 5) In claims 1 to 3, 2 of the aromatic carboxylic acids
A light-shielding material whose valent metal salt is a zinc or nickel metal salt. 6) A light-shielding article obtained by dissolving or dispersing the light-shielding material according to claim 1 in an organic binder and coating it on a support.